Dual hydrogen production apparatus

ABSTRACT

The present invention provides an apparatus for the dual production of hydrogen, wherein organic feed material of a primary hydrogen production apparatus is heated with excess or diverted heat from a secondary hydrogen production apparatus, thereby substantially deactivating or killing methanogens within the organic feed material. Hydrogen producing microorganisms contained or added to the organic feed material metabolize the organic feed material in a bioreactor to produce hydrogen in a primary hydrogen production apparatus. As the methanogens are no longer substantially present to convert produced hydrogen to methane, a biogas that contains hydrogen without substantial methane can be produced.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Patent Application Ser. No. 60/685,851, filed May 31, 2005,entitled “COMBINATION BIOREACTOR AND ELECTROLYZER FOR PRODUCTION OFHYDROGEN”

FIELD OF THE INVENTION

The present invention relates generally to a combination apparatus forconcentrated production of hydrogen from hydrogen producingmicroorganism cultures. More particularly, the invention relates to amethod that dually combines a primary hydrogen production apparatus witha secondary hydrogen production apparatus that is different than theprimary hydrogen production apparatus. The primary hydrogen productionapparatus uses heat or uses heat waste that is produced during typicalusage of the secondary hydrogen production apparatus, thereby reducingenergy costs of the primary hydrogen production apparatus and conservingenergy.

BACKGROUND OF THE INVENTION

The production of hydrogen is an increasingly common and importantprocedure in the world today. Production of hydrogen in the U.S. alonecurrently amounts to about 3 billion cubic feet per year, with outputlikely to increase. Uses for the produced hydrogen are varied, rangingfrom uses in welding to production of hydrochloric acid. An increasinglyimportant use of hydrogen relates to the production of alternative fuelsfor machinery such as motor vehicles. Successful use of hydrogen as analternative fuel can provide substantial benefits to the world at large.This is important not only in that the hydrogen can be formed withoutdependence on the location of specific oils or other ground resources,but in that burning of hydrogen for fuel is atmospherically clean.Essentially, no carbon dioxide or greenhouse gasses are produced duringthe burning. Thus, production of hydrogen is an environmentallydesirable goal.

Creation of hydrogen from certain methods and apparatuses are generallyknown. For example, electrolysis, which generally involves the use ofelectricity to decompose water into hydrogen and oxygen, is a commonlyused process. Significant energy, however, is required to produce theneeded electricity to perform the process. Similarly, steam reforming isanother expensive method requiring fossil fuels as an energy source. Ascould be readily understood, the environmental benefits of producinghydrogen are at least partially offset when using a process that usespollution-causing fuels as an energy source for the production ofhydrogen.

New methods of hydrogen generation are therefore needed. One possiblemethod is to create hydrogen in a biological system by convertingorganic matter into hydrogen gas. The creation of a biogas that issubstantially hydrogen can theoretically be achieved in a bioreactor,wherein hydrogen producing microorganisms and an organic feed materialare held in an environment favorable to hydrogen production. Substantialand useful creation of hydrogen gas from microorganisms, however, isproblematic. The primary obstacle to sustained production of usefulquantities of hydrogen by micro-organisms has been the eventual stoppageof hydrogen production generally coinciding with the appearance ofmethane. This occurs when methanogenic microorganisms invades thebioreactor environment converting hydrogen to methane. This processoccurs naturally in anaerobic environments such as marshes, swamps, andpond sediments. As the appearance of methanogens in a biological systemhas previously been largely inevitable, continuous production ofhydrogen from hydrogen producing micro-organisms has been unsuccessfulin the past.

Microbiologists have for many years known of organisms which generatehydrogen as a metabolic by-product. Two reviews of this body ofknowledge are Kosaric and Lyng (1988) and Nandi and Sengupta (1998).Among the various organisms mentioned, the heterotrophic facultativeanaerobes are of interest in this study, particularly those in the groupknown as the enteric microorganisms. Within this group are themixed-acid fermenters, whose most well known member is Escherichia coli.While fermenting glucose, these micro-organisms split the glucosemolecule forming two moles of pyruvate (Equation 1); an acetyl group isstripped from each pyruvate fragment leaving formic acid (Equation 2),which is then cleaved into equal amounts of carbon dioxide and hydrogenas shown in simplified form below Equation 3).Glucose→2 Pyruvate  (1)2 Pyruvate+2 Coenzyme A→2 Acetyl-CoA+2 HCOOH  (2)2 HCOOH→2H₂+2 CO₂  (3)

Thus, during this process, one mole of glucose produces two moles ofhydrogen gas. Also produced during the process are acetic and lacticacids, and minor amounts of succinic acid and ethanol. Other entericmicroorganisms (the 2, 3 butanediol fermenters) use a different enzymepathway which causes additional CO₂ generation resulting in a 6:1 ratioof carbon dioxide to hydrogen production (Madigan et al., 1997). Afterthis process, the hydrogen is typically converted into methane bymethanogens.

There are many sources of waste organic matter which could serve as asubstrate for this microbial process. One such material would beorganic-rich industrial wastewaters, particularly sugar-rich waters,such as fruit and vegetable processing wastes. Other sources includeagricultural residues and other organic waste such as sewage andmanures.

Electrolysis is generally a chemical process in which chemically bondedelements are separated by passing an electrical current through them. Animportant application of electrolysis is in the separation of water intohydrogen and oxygen by the equation 2H₂O→2H₂+O₂. This reaction can occuron a highly simplified level, for example, by running two leads from atypical battery into water held in a cup. In this instance, aselectricity is passed from one lead to another, preferably with the aidof a water soluble electrolyte, hydrogen and oxygen bubbles can be seenbubbling up from the water.

In more industrial applications, electrolysis can create hydrogen on alarger scale in an electrolyzer. While an electrolyzer is functional atroom temperature, doing so at an efficient level requires a high levelof electrical energy. High temperature electrolyzers are more efficientthan traditional room-temperature electrolyzers because some of theenergy is supplied as heat, which is cheaper than electricity, andbecause the electrolysis reaction is more efficient at highertemperatures. Indeed, at 2500° C., electrical input is unnecessarybecause water breaks down to hydrogen and oxygen through thermolysis. Assuch temperatures are impractical, however; high temperatureelectrolyzers operate at about 100 to 1000° C. At higher temperatureoperating rates, lower levels of energy are required.

Typical high temperature electrolyzers convey steam or super-heatedwater into an electrolytic cell having an anode and a cathode. This mayoccur in combination with hydrogen, for example, at about a 50-50 ratioof steam to hydrogen. The steam or water is split within the cell suchthat oxygen moves toward the anode and hydrogen moves toward thecathode. Remaining steam (if used), prior existing hydrogen and producedhydrogen exit the cell together, wherein hydrogen which can be separatedfrom the steam by a condenser or other like apparatus. In either case,there is never a 100% efficient conversion of the water or steam tohydrogen, resulting in left over heated steam, water and/or oxygen.

In other industrial applications, hydrogen is produced through otherreactions that occur at increased temperature levels. Usually in theseinstances, for economic production, high temperatures are required toensure rapid throughput and high conversion efficiencies. (Transport andthe Hydrogen Economy, UIC Nuclear Issues Briefing Paper # 73, October2005) For example, in an sulfur-iodine system, sulfuric acid is heatedunder high temperature (800-1000° C.) and low pressure. The sulfuricacid breaks sown into water, oxygen and sulfur oxide, which combine withiodine to form 2HI and sulfuric acid. The 2HI reacts with water andsulfur dioxide to under temperatures of about 350° C. to producehydrogen and sulfur dioxide. The net result of the equation is the sameas electrolysis: 2H₂O→2H₂+O₂. However, as not all compounds areconverted, this process also results in heat or excess heat in the formof several solutions or gasses of elevated temperatures at elevatedtemperatures.

New apparatuses for hydrogen generation are therefore needed thatproduce substantial and useful levels of hydrogen in an inexpensive,environmentally sound apparatus that additionally dually combinediffering hydrogen production apparatuses.

SUMMARY OF THE INVENTION

Therefore, it is an object of the present invention to create anapparatus of dual hydrogen production wherein hydrogen is produced in aprimary system with hydrogen producing microorganisms by utilizing heator heat waste from a secondary hydrogen production apparatus such aselectrolysis to deactivate or kill methanogens that would otherwisemetabolize the produced hydrogen.

It is a further object of the invention to provide an apparatus fordually producing hydrogen An apparatus for dually producing hydrogen,comprising: a secondary hydrogen production apparatus including anapparatus that breaks down chemical compounds, wherein hydrogen isproduced from one or a series of reactions using heated liquids, vaporsor gases, a primary hydrogen production apparatus operably combined withthe secondary hydrogen production apparatus, the primary hydrogenproduction apparatus including a bioreactor adapted to produce hydrogenfrom microorganisms metabolizing an organic feed material, and a heatexchanger operably associated with the primary and secondary hydrogenproduction apparatuses such that heat from the secondary hydrogenproduction apparatus is transferred to the primary hydrogen productionapparatus.

It is a further object of the invention to provide an apparatus whereina bioreactor is readily combinable and proximate with secondary hydrogenproduction apparatus of varying types, the bioreactor utilizing heat orheat waste from the secondary hydrogen production apparatus with a heatexchanger bridge, wherein the hydrogen is not substantially converted tomethane subsequent to production.

It is a further object of the invention to heat the organic feedmaterial prior to entry into the bioreactor, wherein heating is achievedin any one or a multiplicity of upstream containers or passages, suchthat heating the organic feed material at temperatures of about 60 to100° C. kills or deactivates methanogens while leaving hydrogenproducing microorganisms substantially intact.

These and other objects of the present invention will become morereadily apparent from the following detailed description and appendedclaims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a plan view of a primary hydrogen production apparatusproximate the secondary hydrogen production apparatus.

FIG. 2 is a side view of one embodiment of the bioreactor.

FIG. 3 is a plan view the bioreactor.

FIG. 4 is a plan view of a secondary hydrogen production apparatusproximate the primary hydrogen production apparatus.

FIG. 5 is a plan view of a high temperature secondary hydrogenproduction apparatus proximate the primary hydrogen productionapparatus.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

As used herein, the term “microorganisms” include bacteria andsubstantially microscopic cellular organisms.

As used herein, the term “hydrogen producing microorganisms” includesmicroorganisms that metabolize an organic substrate in one or a seriesof reactions that ultimately form hydrogen as one of the end products.

As used herein, the term “methanogens” refers to microorganisms thatmetabolize hydrogen in one or a series of reactions that produce methaneas one of the end products.

As used herein, the term “primary hydrogen production apparatus” refersto a hydrogen producing process from hydrogen producing microorganismsin a bioreactor and related preparatory steps.

As used herein, the term “secondary hydrogen production apparatus”refers to a hydrogen producing process other than a bioreactor hydrogenproducing process wherein heat waste resultant from the dual hydrogenproducing process is used in the primary hydrogen production apparatus.

As used herein, the term “heat waste” refers to heat that is produced bydual hydrogen producing process that is otherwise not recycled into thedual hydrogen producing process such as excess heat or aqueous orgaseous compounds that have elevated temperatures, wherein some of theheat is diverted into another hydrogen producing process.

A dual hydrogen producing apparatus 100 in accordance with the presentinvention is shown in FIG. 1, wherein primary hydrogen productionapparatus 96 is shown in detail. As shown in FIG. 1, primary hydrogenproduction apparatus 96 includes bioreactor 10, heat exchanger 12,optional equalization tank 14 and reservoir 16. Apparatus 100 furtherincludes secondary hydrogen production apparatus 50, and passage 44bridging primary hydrogen production apparatus 96 and secondary hydrogenproduction apparatus 50. Apparatus 100 produces gas in bioreactor 10,wherein the produced gas contains hydrogen and does not substantiallyinclude any methane. The hydrogen containing gas is produced by themetabolism of an organic feed material by hydrogen producingmicroorganisms.

In preferred embodiments, organic feed material is a sugar containingorganic feed material. In further preferred embodiments, the organicfeed material is industrial wastewater or effluent product that isproduced during routine formation of fruit and/or vegetable juices, suchas grape juice. In additional embodiments, wastewaters rich not only insugars but also in protein and fats could be used, such as milk productwastes. The most complex potential source of energy for this processwould be sewage-related wastes, such as municipal sewage sludge andanimal manures. However, any feed containing organic material is usablein hydrogen production apparatus 100. Hydrogen producing microorganismscan metabolize the sugars in the organic feed material under thereactions:Glucose→2 Pyruvate  (1)2 Pyruvate+2 Coenzyme A→2 Acetyl-CoA+2 HCOOH  (2)2 HCOOH→2H₂+2 CO₂  (3)

During this process, one mole of glucose produces two moles of hydrogengas and carbon dioxide. In alternate embodiments, other organic feedmaterials include agricultural residues and other organic wastes such assewage and manures. Typical hydrogen producing microorganisms are adeptat metabolizing the high sugar organic waste into bacterial wasteproducts. The wastewater may be further treated by aerating, dilutingthe solution with water or other dilutants, adding compounds that cancontrol the pH of the solution or other treatment step. For example, thesolution may be supplemented with phosphorus (NaH₂PO₄) or yeast extract.

Organic feed material provides a plentiful feeding ground for hydrogenproducing microorganisms and is naturally infested with thesemicroorganisms. While hydrogen producing microorganisms typically occurnaturally in an organic feed material, the organic feed material ispreferably further inoculated with hydrogen producing microorganisms inan inoculation step. The inoculation may be an initial, one-timeaddition to bioreactor 10 at the beginning of the hydrogen productionprocess. Further inoculations, however, may be added as desired. Theadded hydrogen producing microorganisms may include the same types ofmicroorganisms that occur naturally in the organic feed material. Inpreferred embodiments, the hydrogen producing microorganisms, whetheroccurring naturally or added in an inoculation step, are preferablymicroorganisms that thrive in pH levels of about 3.5 to 6.0 and cansurvive in temperature of 60-100° F. or, more preferably, 60-75°. Thesehydrogen producing microorganisms include, but are not limited to,Clostridium sporogenes, Bacillus licheniformis and Kleibsiella oxytoca.Hydrogen producing microorganisms can be obtained from a microorganismalculture lab or like source. Other hydrogen producing microorganisms ormicroorganisms known in the art, however, can be used within the spiritof the invention. The inoculation step can occur in bioreactor 10 orelsewhere in the apparatus, for example, recirculation system 58.

Reservoir 16 is a container known in the art that can contain an organicfeed material. The size, shape, and material of reservoir 16 can varywidely within the spirit of the invention. In one embodiment, reservoir16 is one or a multiplicity of storage tanks that are adaptable toreceive, hold and store the organic feed material when not in use,wherein the one or a multiplicity of storage tanks may be mobile. Inpreferred embodiments, reservoir 16 is a wastewater well that isadaptable to receive and contain wastewater and/or effluent from anindustrial facility 50. In further preferred embodiments, reservoir 16is adaptable to receive and contain wastewater that is effluent from ajuice manufacturing industrial facility 50, such that the effluent heldin the reservoir is a sugar rich juice sludge.

Organic feed material contained in reservoir 16 can be removed throughpassage 22 with pump 28. Pump 28 is in operable relation to reservoir 16such that it aids removal movement of organic feed material 16 intopassage 22 at a desired, adjustable flow rate, wherein pump 28 can beany pump known in the art suitable for pumping liquids. In a preferredembodiment, pump 28 is a submersible sump pump. Reservoir 16 may furtherinclude a low pH cutoff device 52, such that exiting movement intopassage 22 of the organic feed material is ceased if the pH of theorganic feed material is outside of a desired range. The pH cutoffdevice 52 is a device known in the art operably related to reservoir 16and pump 28. If the monitor detects a pH of a solution in reservoir 16out of range, the device ceases operation of pump 28. The pH cut off inreservoir 16 is typically greater than the preferred pH of bioreactor10. In preferred embodiments, the pH cutoff 52 is set between about 7and 8 pH. In alternate embodiments, particularly when reservoir 16 isnot adapted to receive effluent from an industrial facility 50, the pHcutoff device is not used.

Passage 22 provides further entry access into equalization tank 14 orheat exchanger 12. Equalization tank is an optional intermediarycontainer for holding organic feed material between reservoir 16 andheat exchanger 12. Equalization tank 14 provides an intermediarycontainer that can help control the flow rates of organic feed materialinto heat exchanger 12 by providing a slower flow rate into passage 20than the flow rate of organic feed material into the equalization tankthrough passage 22. The equalization tank can be formed of an), materialsuitable for holding and treating the organic feed material. In thepresent invention, equalization tank 14 is constructed of high densitypolyethylene materials. Other materials include, but are not limited to,metals or acrylics. Additionally, the size and shape of equalizationtank 14 can vary widely within the spirit of the invention depending onthroughput and output and location limitations. In preferredembodiments, equalization tank 14 further includes a low level cut-offpoint device 56. The low-level cut-off point device ceases operation ofpump 26 if organic feed material contained in equalization tank 14 fallsbelow a predetermined level. This prevents air from entering passage 20.Organic feed material can be removed through passage 20 or throughpassage 24. Passage 20 provides removal access from equalization tank 14and entry access into heat exchanger 12. Passage 24 provides removalaccess from equalization tank 14 of solution back to reservoir 16.Passage 24 provides a removal system for excess organic feed materialthat exceeds the cut-off point of equalization tank 14. Both passage 20and passage 24 may further be operably related to pumps to facilitatemovement of the organic feed material. In alternate embodiments,equalization tank 14 is not used and organic feed material movesdirectly from reservoir 16 to heat exchanger 12. In these embodiments,passages connecting reservoir 16 and heat exchanger 12 are arrangedaccordingly.

The organic feed material is heated prior to conveyance into thebioreactor. The heating can occur anywhere upstream. In one embodiment,the heating is achieved in one or a multiplicity of heat exchangers 12,wherein the organic feed material is heated within the heat exchanger 12by liquids or gasses of elevated temperatures from secondary hydrogenproduction apparatus 50 conveyed through passage 44. Passage 44 mayfurther be associated with a pump device to control flow rates. Afterexiting heat exchanger 12, gases or liquids originally conveyed throughpassage 44 may be discarded through an effluent pipe (not pictured) orrecycled back into the secondary hydrogen production apparatus. Organicfeed solution can be additionally heated at additional or alternatelocations in the hydrogen production apparatus. Passage 20 providesentry access to heat exchanger 12, wherein heat exchanger 12 is anyapparatus known in the art that can contain and heat contents heldwithin it. Passage 20 is preferably operably related to pump 26. Pump 26aids the conveyance of solution from equalization tank 14 or reservoir16 into heat exchanger 12 through passage 20, wherein pump 26 is anypump known in the art suitable for this purpose. In preferredembodiments, pump 26 is an air driven pump for ideal safety reasons.However, motorized pumps are also found to be safe and are likewiseusable.

To allow hydrogen producing microorganisms within the bioreactor 10 tometabolize the organic feed material and produce hydrogen withoutsubsequent conversion of the hydrogen to methane by methanogens,methanogens contained within the organic feed material are substantiallykilled or deactivated. In preferred embodiments, the methanogens aresubstantially killed or deactivated prior to entry into the bioreactor.In further preferred embodiments, methanogens contained within theorganic feed material are substantially killed or deactivated by beingheated under elevated temperatures in heat exchanger 12. Methanogens aresubstantially killed or deactivated by elevated temperatures.Methanogens are generally deactivated when heated to temperatures ofabout 60-75° C. for a period of at least 15 minutes. Additionally,methanogens are generally damaged or killed when heated to temperaturesabove about 90° C. for a period of at least 15 minutes. Heat exchanger12 enables heating of the organic feed material to temperature of about60-100° C. in order to substantially deactivate or kill the methanogenswhile leaving any hydrogen producing microorganisms substantiallyfunctional. This effectively pasteurizes or sterilizes the contents ofthe organic feed material from active methanogens while leaving thehydrogen producing microorganisms intact, thus allowing the producedbiogas to include hydrogen without subsequent conversion to methane. Thesize, shape and numbers of heat exchangers 12 can vary widely within thespirit of the invention depending on throughput and output required andlocation limitations. In preferred embodiments, retention time in heatexchanger 12 is at least 20 minutes. Retention time marks the averagetime any particular part of organic feed material is retained in heatexchanger 12.

At least one temperature sensor 48 monitors a temperature indicative ofthe organic feed material temperature, preferably the temperature levelsof equalization tank 14 and/or heat exchanger 12. In preferredembodiments, an electronic controller is provided having at least onemicroprocessor adapted to process signals from one or a plurality ofdevices providing organic feed material parameter information, whereinthe electronic controller is operably related to the at least oneactuatable terminal and is arranged to control the operation of and tocontrollably heat the heat exchanger 12 and/or any contents therein. Theelectronic controller is located or coupled to heat exchanger 12 orequalization tank 14, or can alternatively be at a third or remotelocation. In alternate embodiments, the controller for controlling thetemperature of heat exchanger 12 is not operably related to temperaturesensor 48.

Passage 18 connects heat exchanger 12 with bioreactor 10. Organic feedmaterial is conveyed into the bioreactor through transport passage 18 ata desired flow rate. System 100 is a continuous flow system with organicfeed material in constant motion between containers such as reservoir16, heat exchanger 12, bioreactor 10, equalization tank 14 ifapplicable, and so forth. Flow rates between the container can varydepending on retention time desired in any particular container. Forexample, in preferred embodiments, retention time in bioreactor 10 isbetween about 6 and 12 hours. To meet this retention time, the flow rateof passage 18 and effluent passage 36 are adjustable as known in the artso that organic feed material, on average, stays in bioreactor 10 forthis period of time.

The organic feed material is conveyed through passage 18 having a firstand second end, wherein passage 18 provides entry access to thebioreactor at a first end of passage 18 and providing removal access tothe heat exchanger 12 at a second end of passage 18. Any type of passageknown in the art can be used, such as a pipe or flexible tube. Thetransport passage may abut or extend within the bioreactor and/or theheat exchanger 12. Passage 18 can generally provide access to bioreactor10 at any location along the bioreactor. However, in preferredembodiments, passage 18 provides access at an upper portion ofbioreactor 10.

Bioreactor 10 provides an anaerobic environment conducive for hydrogenproducing microorganisms to grow, metabolize organic feed material, andproduce hydrogen. While the bioreactor is beneficial to the growth ofhydrogen producing microorganisms and the corresponding metabolism oforganic feed material by the hydrogen producing microorganisms, it ispreferably restrictive to the proliferation of unwanted microorganismssuch as methanogens, wherein methanogens are microorganisms thatmetabolize carbon dioxide and hydrogen to produce methane and water.Methanogens are obviously unwanted as they metabolize hydrogen. Ifmethanogens were to exist in substantial quantities in bioreactor 10,hydrogen produced by the hydrogen producing bacteria will subsequentlybe converted to methane, reducing the percentage of hydrogen in theproduced gas.

Bioreactor 10 can be any receptacle known in the art for holding anorganic feed material. Bioreactor 10 is substantially airtight,providing an anaerobic environment. Bioreactor 10 itself may containseveral openings. However, these openings are covered with substantiallyairtight coverings or connections, such as passage 18, thereby keepingthe environment in bioreactor 10 substantially anaerobic. Generally, thereceptacle will be a limiting factor for material that can be produced.The larger the receptacle, the more hydrogen producing bacteriacontaining organic feed material, and, by extension, hydrogen, can beproduced. Therefore, the size and shape of the bioreactor can varywidely within the sprit of the invention depending on throughput andoutput and location limitations.

A preferred embodiment of a bioreactor is shown in FIG. 2. Bioreactor 80can be formed of any material suitable for holding an organic feedmaterial and that can further create an airtight, anaerobic environment.In the present invention, bioreactor 10 is constructed of high densitypolyethylene materials. Other materials, including but not limited tometals or plastics can similarly be used. A generally silo-shapedbioreactor 80 has about a 300 gallon capacity with a generally conicalbottom 84. Stand 82 is adapted to hold cone bottom 84 and thereby holdbioreactor 80 in an upright position. The bioreactor 80 preferablyincludes one or a multiplicity of openings that provide a passage forsupplying or removing contents from within the bioreactor. The openingsmay further contain coverings known in the art that cover and uncoverthe openings as desired. For example, bioreactor 80 preferably includesa central opening covered by lid 86. In alternate embodiments of theinvention, the capacity of bioreactor 80 can be readily scaled upward ordownward depending on needs or space limitations.

To maintain the solution volume level at a generally constant level, thebioreactor preferably provides a system to remove excess solution, asshown in FIGS. 1 and 3. In the present embodiment, the bioreactorincludes effluent passage 36 having an open first and second end thatprovides a passage from inside bioreactor 10 to outside the bioreactor.The first end of effluent passage 36 may abut bioreactor 10 or extendinto the interior of bioreactor 10. If effluent passage 36 extends intothe interior of passage 10, the effluent passage preferably extendsupwards to generally upper portion of bioreactor 10. When bioreactor 10is filled with organic feed material, the open first end of the effluentpassage allows an excess organic feed material to be received byeffluent passage 36. Effluent passage 36 preferably extends frombioreactor 10 into a suitable location for effluent, such as a sewer oreffluent container, wherein the excess organic feed material will bedeposited through the open second end.

Bioreactor 10 preferably contains one or a multiplicity of substrates 90for providing surface area for attachment and growth of bacterialbiofilms. Sizes and shapes of the one or a multiplicity of substrates 90can vary widely, including but not limited to flat surfaces, pipes,rods, beads, slats, tubes, slides, screens, honeycombs, spheres, objectwith latticework, or other objects with holes bored through the surface.Numerous substrates can be used, for example, hundreds, as needed. Themore successful the biofilm growth on the substrates, the more fixedstate hydrogen production will be achieved. The fixed nature of thehydrogen producing microorganisms provide the sustain production ofhydrogen in the bioreactor.

Substrates 90 preferably are substantially free of interior spaces thatpotentially fill with gas. In the present embodiment, the bioreactorcomprises about 100-300 pieces of 1″ plastic media to provide surfacearea for attachment of the bacterial biofilm. In one embodiment,substrates 90 are Flexiring™ Random Packing (Koch-Glitsch.) Somesubstrates 90 may be retained below the liquid surface by a retainingdevice, for example, a perforated acrylic plate. In this embodiment,substrates 90 have buoyancy, and float on the organic feed material.When a recirculation system is operably, the buoyant substrates stay atthe same general horizontal level while the organic feed materialcirculates, whereby providing greater access to the organic feedmaterial by hydrogen producing microorganism- and nonparaffinophilicmicroorganism-containing biofilm growing on the substrates.

In preferred embodiments, a recirculation system 58 is provided inoperable relation to bioreactor 10. Recirculation system 58 enablescirculation of organic feed material contained within bioreactor 10 byremoving orgYanic feed material at one location in bioreactor 10 andreintroduces the removed organic feed material at a separate location inbioreactor 10, thereby creating a directional flow in the bioreactor.The directional flow aids the microorganisms within the organic feedmaterial in finding food sources and substrates on which to grownbiofilms. As could be readily understood, removing organic feed materialfrom a lower region of bioreactor 10 and reintroducing it at an upperregion of bioreactor 10 would create a downward flow in bioreactor 10.Removing organic feed material from an upper region of bioreactor 10 andreintroducing it at a lower region would create an up-flow in bioreactor10.

In preferred embodiments, as shown in FIG. 1, recirculation system 58 isarranged to produce an up-flow of any solution contained in bioreactor10. Passage 60 provides removal access at a higher point than passage 62provides entry access. Pump 30 facilitates movement from bioreactor 10into passage 60, from passage 60 into passage 62, and from passage 62back into bioreactor 10, creating up-flow movement in bioreactor 10.Pump 30 can be any pump known in the art for pumping organic feedmaterial. In preferred embodiments, pump 30 is an air driven centrifugalpump. Other arrangements can be used, however, while maintaining thespirit of the invention. For example, a pump could be operably relatedto a single passage that extends from one located of the bioreactor toanother.

Bioreactor 10 may optionally be operably related to one or amultiplicity of treatment apparatuses for treating organic feed materialcontained within bioreactor 10 for the purpose of making the organicfeed material more conducive to proliferation of hydrogen producingmicroorganisms. The one or a multiplicity of treatment apparatusesperform operations that include, but are to limited to, aerating theorganic feed material, diluting the organic feed material with water orother dilutant, controlling the pH of the organic feed material, andadding additional chemical compounds to the organic feed material. Theapparatus coupled to the bioreactor can be any apparatuses known in theart for incorporating these treatments. For example, in one embodiment,a dilution apparatus is a tank having a passage providing controllableentry access of a dilutant, such as water, into bioreactor 10. Anaerating apparatus is an apparatus known in the art that provides a flowof gas into bioreactor 10, wherein the gas is typically air. A pHcontrol apparatus is an apparatus known in the art for controlling a pHof a solution. Additionally chemical compounds added by treatmentapparatuses include anti-fungal agents, phosphorous supplements, yeastextract or hydrogen producing microorganism inoculation. In otherembodiments, the one or a multiplicity of treatment apparatuses may beoperably related to other parts of the bioreactor system. For example,in one example, the treatment apparatuses are operably related toequalization tank 14 or recirculation system 58. In still otherembodiments, multiple treatment apparatus of the same type may belocated at various points in the bioreactor system to provide treatmentsat desired locations.

Certain hydrogen producing bacteria proliferate in pH conditions thatare not favorable to methanogens, for example, Kleibsiella oxytoca.Keeping organic feed material contained within bioreactor 10 within thisfavorable pH range is conducive to hydrogen production. In preferredembodiments, pH controller 34 monitors the pH level of contentscontained within bioreactor 10. In preferred embodiments, the pH of theorganic feed material in bioreactor 10 is maintained at about 3.5 to 6.0pH, most preferably at about 4.5 to 5.5 pH, as shown in Table 2. Infurther preferred embodiments, pH controller 34 controllably monitorsthe pH level of the organic feed material and adjustably controls the pHof the solution if the solution falls out of or is in danger of fallingout of the desired range. As shown in FIG. 1, pH controller 34 monitorsthe pH level of contents contained in passage 62, such as organic feedmaterial, with pH sensor 64. As could readily be understood, pHcontroller 34 can be operably related to any additional or alternativelocation that potentially holds organic feed material, for example,passage 60, passage 62 or bioreactor 10 as shown in FIG. 3.

If the pH of the organic feed material falls out of a desired range, thepH is preferably adjusted back into the desired range. Precise controlof a pH level is necessary to provide an environment that enables atleast some hydrogen producing bacteria to function while similarlyproviding an environment unfavorable to methanogens. This enables thenovel concept of allowing microorganism reactions to create hydrogenwithout subsequently being overrun by methanogens that convert thehydrogen to methane. Control of pH of the organic feed material in thebioreactor can be achieved by any means known in the art. In oneembodiment, a pH controller 34 monitors the pH and can add a pH controlsolution from container 54 in an automated manner if the pH of thebioreactor solution moves out of a desired range. In a preferredembodiment, the pH monitor controls the bioreactor solution's pH throughautomated addition of a sodium or potassium hydroxide solution. One suchapparatus for achieving this is an Etatron DLX pH monitoring device.Preferred ranges of pH for the bioreactor solution is between about 3.5and 6.0, with a more preferred range between about 4.0 and 5.5 pH.

The hydrogen producing reactions of hydrogen producing bacteriametabolizing organic feed material in bioreactor 10 can further bemonitored by oxidation-reduction potential (ORP) sensor 32. ORP sensor32 monitors redox potential of organic feed material contained withinbioreactor 10. Once ORP drops below about −200 mV, gas productioncommences. Subsequently while operating in a continuous flow mode, theORP was typically in the range of −300 to −450 mV.

In one embodiment, the wastewater is a grape juice solution preparedusing Welch's Concord Grape Juice™ diluted in tap water at approximately32 mL of juice per Liter. The solution uses chlorine-free tap water oris aerated previously for 24 hours to substantially remove chlorine. Dueto the acidity of the juice, the pH of the organic feed material istypically around 4.0. The constitutional make-up of the grape juicesolution is shown in Table 1. TABLE 1 Composition of concord grapejuice. Source: Welch's Company, personal comm., 2005. Concentration(unit indicated) Constituent Mean Range Carbohydrates¹ 15-18% glucose6.2% 5-8% fructose 5.5% 5-8% sucrose 1.8% 0.2-2.3% maltose 1.9%   0-2.2%sorbitol 0.1%   0-0.2% Organic Acids¹ 0.5-1.7% Tartaric acid 0.84%  0.4-1.35% Malic acid 0.86%  0.17-1.54% Citric acid 0.044%  0.03-0.12%Minerals¹ Calcium 17-34 mg/L Iron 0.4-0.8 mg/L Magnesium 6.3-11.2 mg/LPhosphorous 21-28 mg/L Potassium 175-260 mg/L Sodium 1-5 mg/L Copper0.10-0.15 mg/L Manganese 0.04-0.12 mg/L Vitamins¹ Vitamin C 4 mg/LThiamine 0.06 mg/L Riboflavin 0.04 mg/L Niacin 0.2 mg/L Vitamin A 80I.U. pH 3.0-3.5 Total solids 18.5%¹additional trace constituents in these categories may be present.

Bioreactor 10 further preferably includes an overflow cut-off switch 66to turn off pump 26 if the solution exceeds or falls below a certainlevel in the bioreactor.

Bioreactor 10 further includes an apparatus for capturing the hydrogencontaining gas produced by the hydrogen producing bacteria. Capture andcleaning methods can vary widely within the spirit of the invention. Inthe present embodiment, as shown in FIG. 1, gas is removed frombioreactor 10 through passage 38, wherein passage 38 is any passageknown in the art suitable for conveying a gaseous product. Pump 40 isoperably related to passage 38 to aid the removal of gas from bioreactor10 while maintaining a slight negative pressure in the bioreactor. Inpreferred embodiments, pump 40 is an air driven pump. The gas isconveyed to gas scrubber 42, where hydrogen is separated from carbondioxide. Other apparatuses for separating hydrogen from carbon dioxidemay likewise be used. The volume of collected gas can be measured bywater displacement before and after scrubbing with concentrated NaOH.Samples of scrubbed and dried gas may be analyzed for hydrogen andmethane by gas chromatography with a thermal conductivity detector (TCD)and/or with a flame ionization detector (FID). Both hydrogen and methanerespond in the TCD, but the response to methane is improved in the FID(hydrogen is not detected by an FID, which uses hydrogen as a fuel forthe flame).

Exhaust system 70 exhausts gas. Any exhaust system known in the art canbe used. In a preferred embodiment, as shown in FIG. 1, exhaust systemincludes exhaust passage 72, backflow preventing device 74, gas flowmeasurement and totalizer 76, and air blower 46.

The organic feed material may be further inoculated in an initialinoculation step with one or a multiplicity of hydrogen producingbacteria, such as Clostridium sporogenes, Bacillus licheniformiis andKleibsiella oxytoca, while contained in bioreactor 10. These hydrogenproducing bacteria are obtained from a bacterial culture lab or likesource. Alternatively, the hydrogen producing bacteria that occurnaturally in the waste solution can be used without inoculating thesolution. In further alternative embodiments, additional inoculationscan occur in bioreactor 10 or other locations of the apparatus, forexample, heat exchanger 12, equalization tank 14 and reservoir 16.

In the present embodiment, the preferred hydrogen producing bacteria isKleibsiella oxytoca, a facultative enteric bacterium capable of hydrogengeneration. Kleibsiella oxytoca produces a substantially 1:1 ratio ofhydrogen to carbon dioxide through organic feed material metabolization,not including impurities. The source of both the Kleibsiella ocytoca maybe obtained from a source such yeast extract. In one embodiment, thecontinuous input of seed organisms from the yeast extract in the wastesolution results in a culture of Kleibsiella oxytoca in the bioreactorsolution. Alternatively, the bioreactor may be directly inoculated withKleibsiella oxyfoca. In one embodiment, the inoculum for the bioreactoris a 48 h culture in nutrient broth added to diluted grape juice and thebioreactor was operated in batch mode until gas production commenced.

The heating source preferably is heat exchanger 14 that uses heat orheat waste from dual hydrogen producing apparatus 16 to heat the organicfeed material, wherein passage 44 is a bridge between the primary andsecondary hydrogen production apparatus. Any heat exchanger known in theart designed for efficient heat transfer can be used in the apparatusincluding but not limited to parallel flow, counter flow, cross flow,shell and tube, plate, regenerative, adiabatic wheel, boiler and steamgenerator heat exchangers. Heat exchangers that heat a fluid separatedfrom the heat source by a solid wall are preferred.

The method preferably includes at least one temperature sensor forsensing a temperature indicative of the organic feed materialtemperature. In preferred embodiments, an electronic controller isprovided having at least one microprocessor adapted to process signalsfrom one or a plurality of devices providing organic feed materialparameter information, wherein the electronic controller is connected tothe at least one actuatable terminal and is arranged to control theoperation of and to controllably heat the heat exchanger 12 and/or anycontents therein. The electronic controller operable related to heatexchanger 14 or heat exchanger 12 and may be located or coupled to thoselocations or be at a third or remote location.

A heating source for system 100 preferably is heat exchanger 12 thatuses heat or heat waste from industrial facility 50 to heat the organicfeed material, wherein the heat exchanger is a heat exchanger known inthe art. The heat exchanger can be a liquid phase-liquid phase orgas-phase/liquid phase as dictated by the phase of the heat waste. Atypical heat exchanger, for example, is a shell and tube heat exchangerwhich consists of a series of finned tubes, through which a first fluidruns. A second fluid runs over the finned tubes to be heated or cooled.Another type of heat exchanger is a plate heat exhanger, which directsflow through baffles so that fluids to be ehated and cooled areseparated by plates with very large surface area.

Heat is captured from secondary hydrogen production apparatus 50 and isused to partially or fully heat the organic feed material to thetemperatures of about 60 to 100° C. The secondary hydrogen productionapparatus can include any hydrogen producing apparatus wherein thatincludes heat. In preferred embodiments, the secondary hydrogenproduction apparatus is an apparatus that produces hydrogen with byseparating H₂O into hydrogen or water in one or a series of reactions.In further preferred embodiments, the secondary hydrogen productionapparatus is an electrolyzer or a sulfur-iodine system. In oneembodiment, a steam based high temperature electrolyzer is combined withthe primary hydrogen production apparatus 96 of the invention as shownin FIG. 4. Electrolyzer 114 includes cell 102 having a cathode 104 andan anode 106, wherein applied electrical current 112 is applied to thecell. The cell may further include a membrane 108 as needed. Steam andhydrogen stream 110 is conveyed into cell 102, wherein the steam isheated at a temperature from about 100-1000° C. The amount of energyneeded as a function of temperature is generally known in the art, asshown in Table 4. The thermal and electro forces will cause a portion ofthe water or steam to split, wherein oxygen will pass through ionconducting membrane 108 to the anode side and is removed on that side. Amixture of steam and hydrogen, including hydrogen newly formed fromseparation of the water, exits the cell on the cathode side with heatedtemperatures. The hydrogen can then be removed from the steam with acondenser. The condenser can function as heat exchanger 12 or can be aseparate condenser that functions in tandem with heat exchanger 12.Either way, the heat exchanger 12 obtains heat from the steam that exitscell 102 and uses the heat to dually produce hydrogen in the primaryhydrogen production apparatus by elevate the temperature of organic feedmaterial to about 60 to 100° C.

Alternatively, secondary hydrogen production apparatus is a hightemperature electrolyzer that uses heated water, as in FIG. 5. Here, anelectrical current is applied to cathode 116 and anode 118 under heatedtemperatures of about 100-1000° C., separating a portion of the heatedwater into oxygen and hydrogen. The oxygen migrates to the anode sideacross diaphragm 120, while hydrogen migrates to the cathode side. Heatexchanger 12 can obtain heat from the heated water remaining theelectrolyzer or by the released, heated oxygen.

In further embodiments, the secondary hydrogen production apparatus is asulfur-iodide system. In an sulfur-iodine system, sulfuric acid isheated under high temperatures of about 750-1000° C. and low pressureunder the reaction H₂SO₄→H₂O+SO₂+1/2O₂. In certain embodiments, iodinecan combine with the resultant sulfur dioxide and water under conditionsknown in the art under the reaction I₂+SO₂+2H₂O→2HI+H₂SO₄. The 2HIreacts with water and sulfur dioxide to under temperatures of about 350°C. to produce hydrogen and sulfur dioxide under the reaction 2HI→H₂+I₂.The net result of the process is the same as electrolysis: 2H₂O→2H₂+O₂.None of the reactions occur with 100 percent efficiency, resulting insuper-heated byproducts for heat exchanger 44 to remove heat from inorder to heat organic solution in primary hydrogen production apparatus96. Heat exchanger 14 can use heat from any heat source from thisprocess, for example, the heated H₂SO₄, heated H₂O or oxygen. Regardlessof where heat exchanger 44 acquires heat, the dual method enables twoseparate methods of hydrogen production, wherein the primary system usesheat energy from the secondary system in order to treat organic feedmaterial for use in bioreactor 10.

EXAMPLE 1

The apparatus combines a bioreactor with a high temperatureelectrolyzer. The organic feed material is a grape juice waste productdiluted in tap water at approximately 32 mL of juice per liter. Thesolution uses chlorine-free tap water or is aerated previously for 24hours to substantially remove chlorine. The dilution and aeration occurin a treatment container. The organic feed material is then conveyedinto the heat exchanger 12 through a passage.

The organic feed material is heated in the heat exchanger 12 to about65° C. for about 10 minutes to substantially deactivate methanogens. Theorganic feed material is heated with excess heat from the hightemperature electrolyzer with a heat exchanger. The organic feedmaterial is conveyed through a passage to the bioreactor wherein it isfurther inoculated with Kleibsiella oxytoca. The resultant biogasesproduced by the microorganisms metabolizing the organic feed materialinclude hydrogen without any substantial methane.

EXAMPLE 2

A multiplicity of reactors were initially operated at pH 4.0 and a flowrate of 2.5 mL min⁻¹, resulting in a hydraulic retention time (HRT) ofabout 13 h (0.55 d). This is equivalent to a dilution rate of 1.8 d⁻¹.After one week all six reactors were at pH 4.0, the ORP ranged from −300to −450 mV, total gas production averaged 1.6 L d⁻¹ and hydrogenproduction averaged 0.8 L d⁻¹. The mean COD of the organic feed materialduring this period was 4,000 mg L⁻¹ and the mean effluent COD was 2,800mg L⁻¹, for a reduction of 30%. After one week, the pHs of certainreactors were increased by one half unit per day until the six reactorswere established at different pH levels ranging from 4.0 to 6.5. Overthe next three weeks at the new pH settings, samples were collected andanalyzed each weekday. It was found that the optimum for gas productionin this embodiment was pH 5.0 at 1.48 L hydrogen d⁻¹ (Table 2). This wasequivalent to about 0.75 volumetric units of hydrogen per unit ofreactor volume per day. TABLE 2 Production of hydrogen in 2-L anaerobicbioreactors as a function of pH. Total H2 H2 per gas H2 L/g Sugar pHL/day L/day COD moles/mole 4.0^(a) 1.61 0.82 0.23 1.81 4.5^(b) 2.58 1.340.23 1.81 5.0^(c) 2.74 1.48 0.26 2.05 5.5^(d) 1.66 0.92 0.24 1.896.0^(d) 2.23 1.43 0.19 1.50 6.5^(e) 0.52 0.31 0.04 0.32^(a)mean of 20 data points^(b)mean of 14 data points^(c)mean of 11 data points^(d)mean of 7 data points^(e)mean of 6 data points

Also shown in Table 2 is the hydrogen production rate per g of COD,which also peaked at pH 5.0 at a value of 0.26 L g⁻¹ COD consumed. Todetermine the molar production rate, it was assumed that each liter ofhydrogen gas contained 0.041 moles, based on the ideal gas law and atemperature of 25° C. Since most of the nutrient value in the grapejuice was simple sugars, predominantly glucose and fructose (Table 1above), it was assumed that the decrease in COD was due to themetabolism of glucose. Based on the theoretical oxygen demand of glucose(1 mole glucose to 6 moles oxygen), one gram of COD is equivalent to0.9375 g of glucose. Therefore, using those conversions, the molar H₂production rate as a function of pH ranged from 0.32 to 2.05 moles of H₂per mole of glucose consumed. As described above, the pathwayappropriate to these organisms results in two moles of H₂ per mole ofglucose, which was achieved at pH 5.0. The complete data set is providedin Tables 3a and 3b.

Samples of biogas were analyzed several times per week from thebeginning of the study, initially using a Perkin Elmer Autosystem GCwith TCD, and then later with a Perkin Elmer Clarus 500 GC with TCD inseries with an FID. Methane was never detected with the TCD, but traceamounts were detected with the FID (as much as about 0.05%).

Over a ten-day period, the waste solution was mixed with sludge obtainedfrom a methane-producing anaerobic digester at a nearby wastewatertreatment plant at a rate of 30 mL of sludge per 20 L of diluted grapejuice. There was no observed increase in the concentration of methaneduring this period. Therefore, it was concluded that the preheating ofthe feed to 65° C. as described previously was effective in deactivatingthe organisms contained in the sludge. Hydrogen gas production rate wasnot affected (data not shown).

Using this example, hydrogen gas is generated using a microbial cultureover a sustained period of time. The optimal pH for this cultureconsuming simple sugars from a simulated fruit juice bottling wastewaterwas found to be 5.0. Under these conditions, using plastic packingmaterial to retain microbial biomass, a hydraulic residence time ofabout 0.5 days resulted in the generation of about 0.75 volumetric unitsof hydrogen gas per unit volume of reactor per day.

Whereas particular embodiments of this invention have been describedabove for purposes of illustration, it will be evident to those skilledin the art that numerous variations of the details of the presentinvention may be made without departing from the invention as defined inthe appended claims. TABLE 3a Bioreactor Operating Data GAS Total afterLiquid Readings collection volume scrubbing Effluent NaOH Net Feed DateReactor hours (mL) (mL) (mL) (mL) (mL) ORP pH 14-Nov A 5 540 220 780 0780 −408 4.0 14-Nov B 5 380 220 840 0 840 −413 4.1 14-Nov C 5 350 170870 0 870 −318 4.1 14-Nov D 5 320 130 920 0 920 −372 4.1 14-Nov E 5 240100 920 0 920 −324 4.3 14-Nov F 5 50 25 810 0 810 −329 4.0 15-Nov A 5.5450 230 1120 25 1095 −400 4.0 15-Nov B 5.5 450 235 1180 35 1145 −384 4.015-Nov C 5.5 250 130 640 0 640 −278 4.0 15-Nov E 5.5 455 225 1160 0 1160−435 4.0 15-Nov F 5.5 430 235 1160 0 1160 −312 4.0 16-Nov A 5 380 1901020 27 993 −414 4.0 5-Dec A 4.5 200 110 500 35 465 −439 4.0 18-Nov A 5360 190 200 0 200 −423 4.0 21-Nov A 4 320 170 800 40 760 −429 4.0 22-NovA 3.75 285 190 725 21 704 −432 4.0 29-Nov A 4.25 310 155 750 24 726 −4394.0 2-Dec A 3.75 250 120 660 26 634 −438 4.0 6-Dec A 3 150 75 540 0 540−441 4.0 17-Nov A 5.5 300 160 1010 30 980 −414 4.0 averages 4.81 324 164830 13 817 −392 4.0 16-Nov B 5 400 200 1125 45 1080 −397 4.5 16-Nov D 5400 165 960 60 900 −360 4.5 16-Nov E 5 490 240 1100 72 1028 −324 4.51-Dec B 3.5 500 260 570 45 525 −415 4.5 6-Dec B 3 470 240 650 40 610−411 4.5 21-Nov B 4 560 300 930 50 880 −397 4.5 2-Dec B 3.75 640 320 83050 780 −407 4.5 17-Nov B 5.5 450 220 1165 50 1115 −406 4.5 18-Nov B 5390 220 860 42 818 −406 4.5 22-Nov B 3.75 585 395 835 50 785 −397 4.529-Nov B 4.25 620 320 920 42 878 −410 4.5 5-Dec B 4.5 390 190 750 37 713−417 4.5 16-Nov F 5 400 200 1082 93 989 −324 4.5 16-Nov C 5 400 200 95074 876 −325 4.6 averages 4.45 478 248 909 54 856 −385 4.5 CODPerformance Feed Effluent Removal Loading Consumed Total gas H2 H2 Date(mg/L) (mg/L) (mg/L) (g) (g) L/day L/day L/g COD 14-Nov 4,480 2,2932,187 3.494 1.706 2.59 1.06 0.13 14-Nov 4,480 2,453 2,027 3.763 1.7021.82 1.06 0.13 14-Nov 4,480 2,293 2,187 3.898 1.902 1.68 0.82 0.0914-Nov 4,480 1,920 2,560 4.122 2.355 1.54 0.62 0.06 14-Nov 4,480 2,7731,707 4.122 1.570 1.15 0.48 0.06 14-Nov 3,307 2,080 1,227 2.679 0.9940.24 0.12 0.03 15-Nov 3,307 3,787   (480) 3.621 −0.525 1.96 1.00 −0.4415-Nov 3,307 3,253   54 3.787 0.061 1.96 1.03 3.82 15-Nov 3,307 3,520  (213) 2.116 −0.138 1.09 0.57 −0.95 15-Nov 3,307 3,467   (160) 3.836−0.165 1.99 0.98 −1.21 15-Nov 3,307 3,413   (106) 3.836 −0.123 1.88 1.03−1.91 16-Nov 4,693 3,627 1,066 4.660 1.059 1.82 0.91 0.18 5-Dec 4,2674,160   107 1.984 0.050 1.07 0.59 2.21 18-Nov 3,680 5,227 (1,547) 0.736−0.309 1.73 0.91 −0.61 21-Nov 3,493 3,680   (187) 2.655 −0.142 1.92 1.02−1.20 22-Nov 4,107 2,293 1,813 2.891 1.277 1.82 1.22 0.15 29-Nov 5,0133,520 1,493 3.640 1.084 1.75 0.88 0.14 2-Dec 4,587 3,893   694 2.9080.440 1.60 0.77 0.27 6-Dec 4,853 3,093 1,760 2.621 0.950 1.20 0.60 0.0817-Nov 4,907 3,520 1,387 4.809 1.359 1.31 0.70 0.12 averages 4,092 3,213  879 3.344 0.718 1.61 0.82 0.23 16-Nov 4,693 3,520 1,173 5.068 1.2671.92 0.96 0.16 16-Nov 4,693 3,573 1,120 4.224 1.008 1.92 0.79 0.1616-Nov 4,693 3,413 1,280 4.824 1.315 2.35 1.15 0.18 1-Dec 5,173 3,6801,493 2.716 0.784 3.43 1.78 0.33 6-Dec 4,853 3,360 1,493 2.960 0.9113.76 1.92 0.26 21-Nov 3,493 3,147   346 3.074 0.305 3.36 1.80 0.98 2-Dec4,587 3,413 1,174 3.578 0.915 4.10 2.05 0.35 17-Nov 4,907 2,933 1,9745.471 2.201 1.96 0.96 0.10 18-Nov 3,680 2,960   720 3.010 0.589 1.871.06 0.37 22-Nov 4,107 2,720 1,387 3.224 1.089 3.74 2.53 0.36 29-Nov5,013 3,307 1,707 4.402 1.498 3.50 1.81 0.21 5-Dec 4,267 3,840   4273.042 0.304 2.08 1.01 0.62 16-Nov 4,693 3,093 1,600 4.641 1.582 1.920.96 0.13 16-Nov 4,693 2,933 1,760 4.111 1.541 1.92 0.96 0.13 averages4,539 3,278 1,261 3.883 1.079 2.58 1.34 0.23

TABLE 3b Bioreactor Operating Data Continued GAS Total after LiquidReadings collection volume scrubbing Effluent NaOH Net Feed Date Reactorhours (mL) (mL) (mL) (mL) (mL) ORP pH 17-Nov C 5.5 360 200 840 120 720−344 4.9 18-Nov C 5 370 200 1120 70 1050 −328 4.9 29-Nov C 4.25 415 200920 50 870 −403 4.9 17-Nov E 5.5 490 270 1210 115 1095 −352 5.0 1-Dec D3.5 540 250 710 85 625 −395 5.0 17-Nov F 5.5 475 225 1120 130 990 −3675.0 5-Dec D 4.5 580 310 710 77 633 −423 5.0 6-Dec D 3 450 240 490 43 447−420 5.0 17-Nov D 3.5 680 415 580 83 497 −326 5.0 2-Dec D 3.75 640 340830 66 764 −412 5.0 22-Nov C 3.75 460 295 800 50 750 −349 5.0 averages4.34 496 268 848 81 767 −374.5 5.0 5-Dec C 4.5 470 250 900 103 797 −4295.4 18-Nov F 5 90 45 600 55 545 −451 5.5 21-Nov D 4 130 70 830 80 750−454 5.5 22-Nov D 3.75 360 250 765 69 696 −461 5.5 29-Nov D 4.25 100 50940 100 840 −456 5.5 2-Dec C 3.75 550 290 810 93 717 −430 5.5 6-Dec C 3250 130 570 45 525 −428 5.5 averages 4.04 279 155 774 78 696 −444.1 5.521-Nov E 4 350 250 930 130 800 −400 6.0 22-Nov E 3.75 380 280 820 127693 −411 6.0 29-Nov E 4.25 360 230 870 71 799 −467 6.0 1-Dec E 3.5 420250 770 127 643 −471 6.0 2-Dec E 3.75 280 170 540 85 455 −443 6.0 5-DecE 4.5 410 240 930 156 774 −487 6.0 6-Dec E 3 280 170 660 105 555 −4906.0 averages 3.82 354 227 789 114 674 −453 6.0 29-Nov F 4.25 90 45 870150 720 −501 6.5 2-Dec F 3.75 20 0 810 136 674 −497 6.5 22-Nov F 3.75120 105 790 128 662 −477 6.5 5-Dec F 4.5 10 0 670 121 549 −532 6.5 6-DecF 3 60 50 480 90 390 −515 6.5 21-Nov F 4 200 100 910 150 760 −472 6.5averages 3.88 83 50 755 129 626 −499 6.5 COD Performance Feed EffluentRemoval Loading Consumed Total gas H2 H2 Date (mg/L) (mg/L) (mg/L) (g)(g) L/day L/day L/g COD 17-Nov 4,907 2,880 2,027 3.533 1.459 1.57 0.870.14 18-Nov 3,680 2,480 1,200 3.864 1.260 1.78 0.96 0.16 29-Nov 5,0133,093 1,920 4.362 1.670 2.34 1.13 0.12 17-Nov 4,907 4,747 160 5.3730.175 2.14 1.18 1.54 1-Dec 5,173 3,573 1,600 3.233 1.000 3.70 1.71 0.2517-Nov 4,907 3,760 1,147 4.858 1.135 2.07 0.98 0.20 5-Dec 4,267 3,573694 2.701 0.439 3.09 1.65 0.71 6-Dec 4,853 3,253 1,600 2.169 0.715 3.601.92 0.34 17-Nov 4,907 4,213 694 2.439 0.345 4.66 2.85 1.20 2-Dec 4,5873,787 800 3.504 0.611 4.10 2.18 0.56 22-Nov 4,107 1,280 2,827 3.0802.120 2.94 1.89 0.14 averages 4,664 3,331 1,333 3.579 1.023 2.74 1.480.26 5-Dec 4,267 3,413 854 3.401 0.680 2.51 1.33 0.37 18-Nov 3,680 3,440240 2.006 0.131 0.43 0.22 0.34 21-Nov 3,493 3,360 133 2.620 0.100 0.780.42 0.70 22-Nov 4,107 2,880 1,227 2.858 0.854 2.30 1.60 0.29 29-Nov5,013 3,307 1,707 4.211 1.434 0.56 0.28 0.03 2-Dec 4,587 3,573 1,0143.289 0.727 3.52 1.86 0.40 6-Dec 4,853 3,627 1,226 2.548 0.644 2.00 1.040.20 averages 4,286 3,371 914 2.982 0.636 1.66 0.92 0.24 21-Nov 3,4932,987 506 2.794 0.405 2.10 1.50 0.62 22-Nov 4,107 2,453 1,653 2.8461.146 2.43 1.79 0.24 29-Nov 5,013 1,973 3,040 4.006 2.429 2.03 1.30 0.091-Dec 5,173 2,933 2,240 3.326 1.440 2.88 1.71 0.17 2-Dec 4,587 3,3601,227 2.087 0.558 1.79 1.09 0.30 5-Dec 4,267 3,253 1,014 3.303 0.7852.19 1.28 0.31 6-Dec 4,853 2,293 2,560 2.693 1.421 2.24 1.36 0.12averages 4,499 2,750 1,749 3.033 1.179 2.23 1.43 0.19 29-Nov 5,013 1,7073,307 3.610 2.381 0.51 0.25 0.02 2-Dec 4,587 3,573 1,014 3.092 0.6830.13 0.00 0.00 22-Nov 4,107 2,240 1,867 2.719 1.236 0.77 0.67 0.08 5-Dec4,267 2,827 1,440 2.343 0.791 0.05 0.00 0.00 6-Dec 4,853 2,240 2,6131.893 1.019 0.48 0.40 0.05 21-Nov 3,493 2,613 880 2.655 0.669 1.20 0.600.15 averages 4,387 2,533 1,853 2.745 1.160 0.52 0.31 0.04

SELECTED CITATIONS AND BIBLIOGRAPHY

-   Brosseau. J. D. and J. E. Zajic. 1982a. Continuous Microbial    Production of Hydrogen Gas. Int. J. Hydrogen Energy 7(8): 623-628.-   Cheresources Online Chemical Engineering Information,    http://www.cheresources.com/heat_transfer basics.shtml.-   Brosseau, J. D. and J. E. Zajic. 1982ba. Hydrogen-gas Production    with Citrobacter intermedius and Clostridium pasteurianum. J. Chem.    Tech. Biotechnol. 32:496-502.-   Iyer, P., M. A. Bruns, H. Zhang, S. Van Ginkel, and B. E.    Logan. 2004. Hydrogen gas production in a continuous flow bioreactor    using heat-treated soil inocula. Appi. Microbiol. Biotechnol.    89(1):119-127.-   Kalia, V. C., et al. 1994. Fermentation of biowaste to H2 by    Bacillus licheniformis. World Journal of Microbiol & Biotechnol.    10:224-227.-   Kosaric, N. and R. P. Lyng. 1988. Chapter 5: Microbial Production of    Hydrogen. In Biotechnology, Vol. 6B. editors Rehm & Reed. pp    101-137. Weinheim: Vett.-   Logan, B. E., S.-E. Oh, I. S. Kim, and S. Van Ginkel. 2002.    Biological hydrogen production measured in batch anaerobic    respirometers. Environ. Sci. Technol. 36(11):2530-2535.-   Logan, B. E. 2004. Biologically extracting energy from wastewater:    biohydrogen production and microbial fuel cells. Environ. Sci.    Technol., 38(9):160A-167A-   Madigan, M. T., J. M. Martinko, and J. Parker. 1997. Brock Biology    of Microorganisms, Eighth Edition, Prentice Hall, N.J.-   Nandi, R. and S. Sengupta. 1998. Microbial Production of Hydrogen:    An Overview. Critical Reviews in Microbiology, 24(1):61-84.-   Noike et al. 2002. Inhibition of hydrogen fermentation of organic    wastes by lactic acid bacteria. International Journal of Hydrogen    Energy. 27:1367-1372-   Oh. S.-E. S. Van Ginkel, and B. E. Logan. 2003. The relative    effectiveness of pH control and heat treatment for enhancing    biohydrogen gas production. Environ. Sci. Technol.,    37(22):5186-5190.-   Prabha et al. 2003. H₂-Producing bacterial communities from a    heat-treated soil Inoculum. Appl. Microbiol. Biotechnol. 66:166-173-   Wang et al. 2003. Hydrogen Production from Wastewater Sludge Using a    Clostridium Strain. J. Env. Sci. Health. Vol. A38(9):1867-1875-   Yokoi et al. 2002. Microbial production of hydrogen from    starch-manufacturing wastes. Biomass & Bioenergy; Vol. 22    (5):389-396.

1. An apparatus for dually producing hydrogen, comprising: a secondaryhydrogen production apparatus including an apparatus that breaks downchemical compounds, wherein hydrogen is produced from one or a series ofreactions using heated liquids, vapors or gases, a primary hydrogenproduction apparatus operably combined with the secondary hydrogenproduction apparatus, the primary hydrogen production apparatusincluding a bioreactor adapted to produce hydrogen from microorganismsmetabolizing an organic feed material, and a heat exchanger operablyassociated with the primary and secondary hydrogen productionapparatuses such that heat from the secondary hydrogen productionapparatus is transferred to the primary hydrogen production apparatus.2. The apparatus of claim 1, wherein the heated liquids, vapors andgases are selected from the group comprising of water, steam,hydrochloric acid, oxygen and sulfur dioxide.
 3. The apparatus of claim1, wherein the heated liquids, vapors and gases in the secondaryhydrogen production apparatus are at a temperature in a range of about100 to 1000° C.
 4. The apparatus of claim 1, wherein the organic feedmaterial is heated for a period of at least fifteen minutes.
 5. Theapparatus of claim 1, wherein the organic feed material is heated by theheat to a temperature of about 60 to 100° C.
 6. The apparatus of claim1, wherein the organic feed material in the bioreactor has a controlledpH by a pH controlling device.
 7. The apparatus of claim 1, wherein thesecondary hydrogen production apparatus is a steam based hightemperature electrolyzer.
 8. The apparatus of claim 1, wherein thesecondary hydrogen production apparatus is a water based hightemperature electrolyzer.
 9. The apparatus of claim 1, wherein thesecondary hydrogen production apparatus is an apparatus conducive tosulfur iodide processes.
 10. The apparatus of claim 1, wherein theheat-exchanger is a gas/liquid heat exchanger.
 11. The apparatus ofclaim 1 wherein the heat-exchanger is a liquid/liquid heat exchanger.12. The apparatus of claim 1, wherein the primary hydrogen productionapparatus further comprises a passage providing entry access to thebioreactor and providing removal access to the heat exchanger.
 13. Theapparatus of claim 12, further providing treatment means for treating anorganic feed material contained within the primary hydrogen productionapparatus.
 14. The apparatus of claim 12, further comprising anelectronic controller having at least one microprocessor adapted toprocess signals from a one or a plurality of devices providing organicfeed material parameter information, wherein the electronic controlleris connected to the at least one actuatable terminal and is arranged tocontrol the operation of the heat exchanger and the temperature of anycontents therein.
 15. The apparatus of claim 12, further comprising apump operably related to the passage.
 16. An apparatus for duallyproducing hydrogen, comprising: a secondary hydrogen productionapparatus including an electrolyzer, wherein hydrogen is produced fromone or a series of reactions using heated liquids, vapors or gases, aprimary hydrogen production apparatus operably combined with thesecondary hydrogen production apparatus, the primary hydrogen productionapparatus including a bioreactor adapted to produce hydrogen frommicroorganisms metabolizing an organic feed material, and a heatexchanger operably associated with the primary and secondary hydrogenproduction apparatuses such that heat from the secondary hydrogenproduction apparatus is transferred to the primary hydrogen productionapparatus.